Polyazo dyestuffs



POLYAZO DYESTUFF S Hans Baumann, Ludwigshafen (Rhine), Germany, assiguorto Badische Anilin- & Soda-Fabrik Aktiengesellschaft, Ludwigshafen(Rhine), Germany No Drawing. Application August 30, 1955 Serial No.531,574

6- Claims. (Cl. 260-444) This invention relates to new polyazodyestuffs. More particularly, the invention relates to a new class ofpolyazo dyestuffs derived from a4.4-diamino-diphenylmethane-3.3'-dicarboxylic acid and to a process ofmanufacturing these dyestufis.

It is an object of this invention to provide new polyazo dyestuffs, inparticular polyazo dyestutfs for coloring leather.

Another object is to provide polyazo dyestuils derived from a4.4-diamino-diphenylmethane-3.3'-dicarboxylic acid and containing atleast four azo groups and at least two sulfonic acid groups.

A further object of this invention are complex metal compounds, inparticular complex cupric compounds, of said new polyazo dyestufis.

A still further object is to provide a method for preparing thesedyestuffs.

NaOaS- HOOC COOH wherein Z represents a member selected from the groupconsisting of hydrogen, a lower alkyl group, and a phenyl group; A and Beach represent a bivalent radical of a twice-coupling aromatic compoundhaving l-2 aromatic rings, said rings having at least one and not morethan two substituents selected from the group consisting of hydroxy andamino groups, said rings further having O2 sulfonic acid groups, saidrings being otherwise unsubstituted; X and Y each represent a memberselected from the group consisting of a benzene, a naphthalene, and adiphenyl nucleus; L and Q each represent at least one member from thegroup consisting of hydrogen, chloro, hydroxy, nitro, amino, loweralkyl, sulfonic acid, phenylazo, a naphthylazo group, lower alkylN-substituted amino group, and a phenyl N-substituted amino group; a andb represent an integer of 1-3, inclusive; and A, B, X, and Y have atotal of at least two sulfonic acid groups.

The outstanding merit of this new polyazo dyestutf is the fact that theyare in particular in the form of their complex compounds with heavymetal salts, such as copper, cobalt or chromium salts, excellentdyestuffs for leather, and yield thereby deep, dark brown to blackshades having a very good fastness.

atentf O COOH HzN- OH- wherein Z is a hydrogen, phenyl or alkyl radical,and then 0 coupling the resultant tetrazo compound with two mole- H ONH:

cules of aromatic compounds capable of being coupled and which stillcontain at least one azo group each and at least two sulfonic acidgroups together.

According to one embodiment of the invention, the new polyazo dyestuir'smay be obtained by coupling one molecule of the tetrazotized4.4'-diamino-diphenylmethane-3.3-dicarboxylic acid with two molecules ofan arcmatic azo compound which contains an aromatic radical with atleast two coupling directing groups which are hydroxy and/ or aminogroups.

An example of such aromatic azo compounds is the mono azo dyestuliprepared by reacting diazotized p-nitroaniline withl-amino-8-hydroxynaphthalene-3.6-disulfonic acid, the said dyestulfhaving the formula HO HH:

NaOaS SOaNB.

or the disazo dyestuif of the formula 5 SOIN prepared by coupling onemolecule of tetrazotized benzidine with one molecule of1-amino-8-hydroxy naphthalene-3.6-sulfonic acid and one molecule of2-hydroxy naphthalene-3.6-sulfonic acid.

According to another embodiment of the invention, one molecule of thetetrazotized 4.4-diamino-diphenylmethane-3.3-dicarboxylic acid iscoupled first with an aromatic compound (I) which is free from azogroups but contains at least two coupling directing groups which arehydroxy and/ or amino groups, and one molecule of the disazo dyestutfthus obtained is converted then by a further coupling reaction with twomolecules of an aromatic compound (II) into a polyazo dyestutf, theradicals of the aromatic compounds used for the two coupling reactionscontaining together at least two sulfonic acid groups.

If, for the first coupling reaction, aromatic compounds which are freefrom amino groups are used, the second coupling reaction may beperformed with two molecules of any aromatic diazo compound. If,however, the arcmatic compounds used in the first coupling reactioncontain amino groups, the resulting disazo-amino dyestufi? can betetrazotized and coupled with an aromatic compound capable of beingcoupled with a diazo or tetrazo compound.

Suitable 4.4'-diamino-diphenylmethane-3.3-dicarboxylic acids may beprepared by condensing one molecule of anthranilic acid or of itshomologues with one molecule of an aldehyde, such as formaldehyde,acetaldehyde or benzaldehyde, in acid medium as described by Heller andFisselmann (Liebigs Annalen der Chemie, vol. 324 (1902), p. 118). It isalso possible to prepare the 4.4-diaminodiphenylmethane-3.3'-dicarboXylic acids in situ 3 and totetrazotize the raw and unpurified reaction mixture without isolatingthe 4.4'-diaminodiphenylmethane-3.3- dicarboxylic acids.

Compounds which may be coupled with the tetrazotized4.4-diamino-diphenylmethane 3.3'-dicarboxylic acids are compounds of thebenzene and naphthalene series which contain two coupling directinggroups which are hydroxy and/or amino groups such as resorcinol,1.3-diaminobenzene, 1.8-dihydroxynaphthalene monoand disulfonic acids,1.6-dihydroxynaphthalene-3-sulfonic acid, 3-amino phenol,3-hydroxydiphenyl amine or l-amino-8-hydroxy otized with 13.8 parts ofsodium nitrite at a temperature between about and 2 C. The formedtetrazo compound is combined at about 0 C. with a solution of 22.0 partsof resorcinol dissolved in 200 parts of 10% aqueous sodium hydroxidesolution. After the coupling reaction has been completed, the formedintermediate disazo dyestutf is precipitated by the addition ofhydrochloric acid, filtered and dissolved in 600 parts of water whileadding excess sodium carbonate. The diazo compound of parts of metanilicacid is then added to said solution. A tetrakis azo dyestutf having thenaphthalene and their sulfonic acids. formula 0 H H O 0 C O O H 1'10 3Naoas As diazo components which may be coupled onto the disazo dyestuff,formed by the first coupling reaction, where an aromatic compound whichis free from amino groups has been used for this first couplingreaction, the diazotization products of aniline and its homologues andof their nitro or halogenated derivatives, such as nitroanilines andtoluidines, 2.5-dichloro-aniline, sulfanilic and metanilic acids,4-chloroaniline-3-sulfonic acid, aniline- 2.5-disulfonic acid,4-aminoazobenzene-3.4'-disulfonic acid, or of naphthylamines or theirmonoor disulfonic acid derivatives, such as1-aminonaphthalene-4-sulfonic acid or 2-aminonaphthalene-4.S-disulfonicacid may be employed. The selection of this compound is made in such amanner that the polyazo dyestutf formed contains at least two sulfonicacid groups. The term sulfonic acid includes the free sulfonic acids aswell as the salts of these acids, in particular their alkali and ammoniasalts.

If a diamino or hydroxyamino compound, preferably of the benzene ornaphthalene series, has been used for the first coupling reaction withthe tetrazotized 4.4-diaminodiphenylmethane-3.3'-dicarboxylic acid, thiscoupling product may be diazotized or tetrazotized again and coupledthen with an aromatic compound capable of being coupled preferably ofthe benzene or naphthalene series, such as a naphthol, a naphthylamineor a sulfonic acid of these compounds, an amino naphthol or a sulfonicacid thereof, a 1.3-dihydroxy or a 1.3-diamino benzene, a1.3-hydroxyamino benzene or the N-alkyl or N- aryl derivatives of thesecompounds. Care must be taken While performing this reaction that theformed polyazo dyestuffs contain at least two sulfonic acid groups.

The new polyazo dyestuffs may be converted into their complex metaldyestuifs in the conventional manner, for instance, by reacting themwith cupric, cobalt or chromium salts in aqueous solution or suspension,if necessary by adding basic compounds such as ammonia or amines.

The new polyazo dyestuffs and their metal complex compounds areexcellently suitable for dyeing tanned leather irrespective of themanner in which the leather has been tanned. On account of their gooddyeing capacity, they can be used in particular for the production ofsuede leather. Since they have usually a good solubility even in acidbaths, the leathers may also be dyed with these dyestuffs fromconcentrated baths without bronzing the dyed leather.

The following examples are given to illustrate the invention. The partsare given by weight unless otherwise specified.

Example 1 28.6 parts of 4.4-diamino-diphenyl-methane-3.3-dicarboxylicacid are dissolved in 250 parts of water and 50 parts of hydrochloricacid (density 1.16), and tetrazis formed. This dyestuff dyes leather inreddish brown shades with a good fastness. On suede leather buff-fast,deep reddish brown shades are obtained.

Example 2 The intermediate disazo dyestuif of Example 1 is coupled withthe diazo compound of 51 parts of aniline- 2.4 or 2.5-disulfonic acid.The obtained tetrakis azo dyestutf is heated several hours in aqueoussolution with 50 parts of crystalline cobalt-ll-cnloride and 32 parts ofsodium acetate. A cobalt complex compound is formed thereby which dyeschrome tanned leather yellowish brown shades with a good iastness. Thecorresponding copper complex compound yields on leathers, tanned byvarious methods, medium brown shades, the chromium complex compoundsreddish brown shades.

Example 3 A solution of 15.0 parts of anthranilic acid in parts of waterand 25 parts of 36.5% hydrochloric acid is mixed at 70 C. with 58 partsof a 3% aqueous formaldehyde solution. The mixture is stirred at 70 C.for several hours until the condensation is completed, cooled to 0 C.and tetrazotized with 7.5 parts of sodium nitrite. The obtained tetrazocompound is coupled with a solution of 11.0 parts of resorcinol in 200parts of a 5% aqueous sodium hydroxide solution. To the solution of theformed intermediate disazo dyestuif, a solution of 16 parts sodiumbicarbonate in 300 parts of water is added. Then the diazo compound of36 parts of 4-amino-azobenzene-3.4-disulfonic acid is added. The formedhexakis azo dyestulf of the formula I OH is salted out, sucked off, anddissolved in water which contains a small amount of ammonia. A solutionof 25.0 parts of crystalline copper sulfate in excess aqueous ammonia isadded and the polyazo dyestutf converted in its copper complex compoundby heating. This complex benzene is added. By adding gradually asolution of 56 compound dyes leather manufactured by various tanningparts of crystalline sodium acetate in 200 parts of water, processesfast neutral brown shades. the coupling reaction is completed. Theformed tetrazo If instead of 4-amino-azobenzene-3.4'-disulfonic aciddyestuff is sucked off, dissolved in 200 parts of hot water there isused an equivalent amount of an amino azo 5 which contains parts ofwater-free sodium carbonate, dyestuff obtained by coupling diazotized2-naphthyland precipitated then by the addition of sodium chloride.

amine-5.7-disulfonic acid with l-naphthylamine in con- The obtainedtetrazo dyestuff of the formula N Hl HQN G? N oH Hooo OOOH HO L r N=NCH2N=N- Naoss -SO Na NaOgS- SOaNa ventional manner, a polyazo dyestutf ofthe formula NaOaS N= N= -C O O H dyes chrome tanned leather deep brownshades with a Naoa good fastness.

If the l-amino-8-hydroxynaphthalene-3.6-disulfonic acid is replaced byl-amino-8-hydroxynaphthalene-4.6-disulfonic acid, a tetrazo dyestulf isformed which under analogous conditions dyes the leather somewhat more00 OH reddish brown shades.

Example 5 NaOaS- N=N N=N N l i 40 H0 The intermediate disazo dyestutf"of Example 4 is tetrazotized as is described in Example 4, and thencoupled with 22 parts of resorcinol while an excess of so- Na-OKS I Hdium carbonate is added. The formed tetrakis azo dyeis formed; Thecopper complex compound of this dyestuff of the formula OH HO a t-O- NOH HOQC (IJOOH OH N Na QaS S OaNa N303S- SO Na stufi prepared by theusual methods yields fast reddish 59 is sucked off. brown shadeson'leat'her. The dyestuff is dissolved in 2000 parts of water. To Exam[e 4 this solution 52.5 parts of crystalline copper sulfate and p 60parts of crystalline sodium sulfate is added, and then Parts of P Y themixture is heated to about 95 C. for one hour. By boxylic acid aretetrazotized as 111 Example 1 and C011- salting out, a copper complexcompound is isolated which p With Parts of y yp q dyes leather deepneutral brown shades having an excel- 3.6-disulfonic acid in thepresence of excess sodium carl f m bonate. The formed intermediatedisazo .dyestufi is isolated by acidifying and salting out and dissolvedin' 1000 parts of water containing 8 parts,.of a;5 ,0% aqueous 15.0parts of anthranilic acid are condensed in an aque- Example 6 sodiumhydroxide solution. This solution is tetrazotized ous solutioncontaining hydrochloric acid as described in by the addition of 7.5parts of sodium nitrite and 70 parts Example 3, with 5.8 parts of a 30%aqueous formalof 36.5% hydrochloric acid at a temperature of aboutdehyde solution. The condensation product is tetrazo- 5 C. The reactionmixture is stirred for three hours tized and coupled with 31.9 parts ofl-amino-S-hydroxyand the excess of nitrite removed by the addition ofurea. naphthalene-3.6-disulfonic acid in the presence of sodium Then zinaqueonssolution of 22 parts of 1.3-diaminocarbonate. The intermediatedisazo dyestuff is sucked off, dissolve and tetrazotized again andcoupled in an alkaline medium with 19 parts of 3-hydroxy-di-phenylamine.The solution of the formed tetrakis azo dyestutf having the formula N OHHOOC CODE temperature until the condensation is completed. In the stillhot mixture, 400 parts of hydrochloric acid (density 1.085) areintroduced while stirring and the obtained clear solution is diluted bythe addition of water to 1000 parts tO- N NaOaS S OaNa is neutralizedwith sulfonic acid and 27.5 parts of crystal- 15 by volume.

line copper sulfate are added. This solution is then boiled shortly. Theformed copper complex dyestulf is salted out while the solution is stillhot and then sucked off. It dyes chrome tanned leather greenish blackshades having an excellent fastness.

If during the last coupling reaction one-half of the3-hydroxy-diphenylamine is replaced by 5.5 parts of resorcinol, a mixedpolyazo dyestulf of the formula NH-CaH5 HO- -IGT N OH HO O C NELO3SsOaNa is formed which gives a copper complex compound dyeing leatherfastly in deep black shades.

Example 7 137.0 parts of anthranilic acid are mixed with 100 parts ofhydrochloric acid (density 1.085). After the addition of 52.5 parts ofbenzaldehyde and 5.0 parts of HzN O H NaOsS- HOOC S O aNa a 40% sodiumbisulfite solution the mixture is gradually heated while refluxing to atemperature between 100 and 105 C. The mixture is stirred for severalhours at this 200 parts by volume of this solution are then mixed withan aqueous solution of 13.8 parts of sodium nitrite at a temperature ofabout 0 C. The partly separated yellow tetrazo compound is graduallyintroduced into a solution which was obtained by coupling 24.8 parts ofdiazotized p-nitroaniline with 54.6 parts of l-amino 8-hydroxynaphthalene-3.6-disulfonic acid, this acid solution having beenneutralized after the coupling reaction ll OH N S O aNa by the additionof sodium hydroxide. During the introduction of the tetrazo compound,the coupling mixture is kept permanently alkalized by the addition ofsodium carbonate. After the coupling reaction has been completed, theformed dyestuff is salted out from the boiling reaction mixture andsucked off while still hot. The obtained tetrazo dyestuff of the formulaC O OH HO S O'NE dyes chrome tanned grain leather and bark tannedleather the same dark blue shades with good fastness.

A polyazo dyestuff of the formula S O aNa giving similar dark blueshades on leather, is obtained when there is used instead of diazotizedp-nitro-aniline the coupling product of one molecule of tetrazotizedbenzidine and one molecule of Z-hydroxy-naphthalene- 3. 6-disulfonicacid containing still one diazo group.

10 rings being otherwise unsubstituted; X and Y represent a memberselected from the group consisting of a benzene, a naphthalene, and adiphenyl nucleus; L and Q each represent at least one member from thegroup consisting I claim 5 of hydrogen, chloro, hydroxy, nitro, amino,lower alkyl, 1. A member selected from the class consisting of asulfonic.acidphenylazo anaphthylazo group= lower alkyl polyazo d t fi fthe general f l N-substituted amino group, and a phenyl N-substitutedH000 000E amino group; a and b represent an integer of 1-3, inclu- 10sive; and A, B, X, and Y havea total of at least two t-- OH- -N=Nl|3sulfonic acid groups. h N=N-Y(-Q,)s 2. A member from the groupconsisting of the tetrakis a copper complex, a cobalt complex and achromium azo dyestuff of the formula 1 0H H000 00011 HO 1% il l OzNaOsNa complex of said polyazo dyestutf wherein Z represents a memberselected from the group consisting of hydrogen, a lower alkyl group, anda phenyl group; A and B each OH I N ll

8 O Na OsNa represent a bivalent radical of a twice-coupling aromaticcompound having 1-2 aromatic rings, said rings having 45 and its cupriccomplex compound.

3. A member from the group consisting of the tetrakis azo dyestuif ofthe formula HOOC OOOH HO SOINB I SOsNa and its cupric complex compound.

4. A member from the group consisting of the hexakis azo dyestutf of theformula OH HO O C C O OH HO HO N=N CH N=N OH N ll IL f F T Il I S O3N8 NSOaNa SOsNa SOaNa at least one and not more than two substituentsselected 65 from the group consisting of hydroxy and amino groups,

and its cupric complex compound.

5. A member from the group consisting of the tetrakis azo dyestufi' ofthe formula on H(|) HOON N OH i l on H000 20011 H(|) r t -N=N-Oom-N=N-NaOaS som NaOaS- -SOsNa said rings further having 0-2 sulfonic acidgroups, said and its cupric complex compound.

2,835,660 7 1 1 12 6. A member from the group consisting of thetetrakisazo dyestuff of the formula OH HO l H500 N CH H000 00011 H andits cupric complex compound.

References Cited in the file of this patent UNITED STATES PATENTS2,264,682 Trepagnier Dec. 2, 1941 2,384,419 Fleischhauer et a1. Sept. 4,1945 FOREIGN PATENTS 930,409 Germany July 14, 1955

1. A MEMBER SELECTED FROM THE CLASS CONSISTING OF A POLYAZO DYESTUFF OFTHE GENERAL FORMULA